{"title":"调整海泡石负载钌的酸度以增强糠醛催化还原胺化制糠胺","authors":"Kanika Saini, Supan, Neeraj Sharma, Rahul Gautam, Shunmugavel Saravanamurugan","doi":"10.1002/cctc.202500982","DOIUrl":null,"url":null,"abstract":"<p>The catalytic reductive amination of bio-based carbonyls has emerged as a promising route for producing N-containing compounds, having a wide range of applications in pharmaceuticals and agrochemicals. In this work, Ru supported on acid-treated sepiolite (Ru/ASep) is designed for the reductive amination of furfural (FUR) to furfurylamine (FUA) using H<sub>2</sub> and NH<sub>3</sub> as reductant and nitrogen source, respectively. Ru/ASep exhibited two times higher catalytic activity compared to its counterpart, that is, Ru supported on parent sepiolite (Ru/Sep), yielding 98.4% FUA. The NH<sub>3</sub>-temperature-programmed desorption (TPD) and NH<sub>3</sub>-diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy studies show that Ru/ASep exhibited an increase in total acidic sites with relatively more Lewis acidic sites than Ru/Sep, contributing to C═N bond activation and leading to the formation of FUA in high yield. The CO<sub>2</sub>-TPD results indicate that ASep possesses a large amount of basic sites, which contribute to a facile reduction of RuO<sub>x</sub> to Ru<sup>0</sup> in Ru/ASep, as confirmed by H<sub>2</sub>-temperature programmed reduction (TPR) studies. H<sub>2</sub>-TPD studies indicate a higher amount of H<sub>2</sub> activated over Ru/ASep, favoring the intermediate hydrogenation step to form FUA. Furthermore, the poisoning studies with KSCN indicated that Lewis acidic sites on the surface of Ru/ASep played a crucial role in the formation of FUA.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tailoring the Acidity of Ru Supported on Sepiolite for Enhanced Catalytic Reductive Amination of Furfural to Furfurylamine\",\"authors\":\"Kanika Saini, Supan, Neeraj Sharma, Rahul Gautam, Shunmugavel Saravanamurugan\",\"doi\":\"10.1002/cctc.202500982\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The catalytic reductive amination of bio-based carbonyls has emerged as a promising route for producing N-containing compounds, having a wide range of applications in pharmaceuticals and agrochemicals. In this work, Ru supported on acid-treated sepiolite (Ru/ASep) is designed for the reductive amination of furfural (FUR) to furfurylamine (FUA) using H<sub>2</sub> and NH<sub>3</sub> as reductant and nitrogen source, respectively. Ru/ASep exhibited two times higher catalytic activity compared to its counterpart, that is, Ru supported on parent sepiolite (Ru/Sep), yielding 98.4% FUA. The NH<sub>3</sub>-temperature-programmed desorption (TPD) and NH<sub>3</sub>-diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy studies show that Ru/ASep exhibited an increase in total acidic sites with relatively more Lewis acidic sites than Ru/Sep, contributing to C═N bond activation and leading to the formation of FUA in high yield. The CO<sub>2</sub>-TPD results indicate that ASep possesses a large amount of basic sites, which contribute to a facile reduction of RuO<sub>x</sub> to Ru<sup>0</sup> in Ru/ASep, as confirmed by H<sub>2</sub>-temperature programmed reduction (TPR) studies. H<sub>2</sub>-TPD studies indicate a higher amount of H<sub>2</sub> activated over Ru/ASep, favoring the intermediate hydrogenation step to form FUA. Furthermore, the poisoning studies with KSCN indicated that Lewis acidic sites on the surface of Ru/ASep played a crucial role in the formation of FUA.</p>\",\"PeriodicalId\":141,\"journal\":{\"name\":\"ChemCatChem\",\"volume\":\"17 20\",\"pages\":\"\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-08-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemCatChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500982\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemCatChem","FirstCategoryId":"92","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500982","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Tailoring the Acidity of Ru Supported on Sepiolite for Enhanced Catalytic Reductive Amination of Furfural to Furfurylamine
The catalytic reductive amination of bio-based carbonyls has emerged as a promising route for producing N-containing compounds, having a wide range of applications in pharmaceuticals and agrochemicals. In this work, Ru supported on acid-treated sepiolite (Ru/ASep) is designed for the reductive amination of furfural (FUR) to furfurylamine (FUA) using H2 and NH3 as reductant and nitrogen source, respectively. Ru/ASep exhibited two times higher catalytic activity compared to its counterpart, that is, Ru supported on parent sepiolite (Ru/Sep), yielding 98.4% FUA. The NH3-temperature-programmed desorption (TPD) and NH3-diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy studies show that Ru/ASep exhibited an increase in total acidic sites with relatively more Lewis acidic sites than Ru/Sep, contributing to C═N bond activation and leading to the formation of FUA in high yield. The CO2-TPD results indicate that ASep possesses a large amount of basic sites, which contribute to a facile reduction of RuOx to Ru0 in Ru/ASep, as confirmed by H2-temperature programmed reduction (TPR) studies. H2-TPD studies indicate a higher amount of H2 activated over Ru/ASep, favoring the intermediate hydrogenation step to form FUA. Furthermore, the poisoning studies with KSCN indicated that Lewis acidic sites on the surface of Ru/ASep played a crucial role in the formation of FUA.
期刊介绍：
With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.
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